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Polyphosphoinositides (PPIns) are a family of seven lipid messengers that regulate a vast array of signalling pathways to control cell proliferation, migration, survival and differentiation. PPIns are differentially present in various sub-cellular compartments and, through the recruitment and regulation of specific proteins, are key regulators of compartment identity and function. Phosphoinositides and the enzymes that synthesise and degrade them are also present in the nuclear membrane and in nuclear membraneless compartments such as nuclear speckles. Here we discuss how PPIns in the nucleus are modulated in response to external cues and how they function to control downstream signalling. Finally we suggest a role for nuclear PPIns in liquid phase separations that are involved in the formation of membraneless compartments within the nucleus.

The manuscript focuses on the demixing of hyaluronan and alginate in the hydrogel state. Binary solutions of the two polysaccharides have been treated with Ca2+ as the alginate cross-linking ion and the radial distribution of the two components in the hydrogels was measured by means of 1H NMR. These results revealed the presence of alginate-enriched and hyaluronan-enriched domains stemming from a polysaccharide demixing. The hydrogels were characterized by means of uniaxial compression and creep-compliance measurements which showed that the demixing increased the overall resistance of the hydrogel to stress. In addition, due to the viscoelastic properties of hyaluronan, a marked increase of the Newtonian viscosity of the constructs was noticed. The peculiarity of the effect of hyaluronan was demonstrated by the use of an alginate unable to form gel by binding non-calcium binding alginate, i.e. mannuronan, ruling out the effect of viscosity over the time-dependent behavior of the mixed hyaluronan-alginate hydrogels.

We study the interface evolution of a series of periodic Co/Mo2C multilayers as a function of the annealing temperature up to 600{\textdegree}C. Different complementary techniques are implemented to get information on the phenomenon taking place at the interfaces of the stack. The periodical structure of Co/Mo2C multilayer is proven by Time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth profiles which demonstrate the formation of an oxide layer at both air/stack and stack/substrate interfaces. From Nuclear magnetic resonance (NMR) spectra, we observed the intermixing phenomenon of Co and C atoms for the as-deposited sample, and then at annealing temperature above 300{\textdegree}C Co and C atoms separate from their mixed regions. Comparison of NMR results between Co/Mo 2 C and Co/C references confirms this phenomenon. This is in agreement with x-ray emission spectroscopy (XES) measurements. Furthermore the calculation of the Co-C, Co-Mo and Mo-C mixing enthalpy using Miedema's model gives a proof of the demixing of Co and C atoms present within the stacks above 300{\textdegree}C. From the transmission electron microscopy (TEM) analysis, we found the presence of some crystallites within the as-deposited sample as well as the mainly amorphous nature of all layers. This is confirmed using x-ray diffraction (XRD) patterns which also demonstrate the growth of crystallites induced upon annealing., Published in Applied Surface Science 331, 8-16 (2015). http://dx.doi.org/10.1016/j.apsusc.2014.12.055

International audience; The sintering behaviour of Pd or Pt loaded ceria-zirconia solid solutions of nominal composition Ce0.50Zr0.50O2 and Ce0.68Zr0.32O2 was studied under oxidising conditions. Calcination treatments were carried out under controlled oxidising atmosphere for periods of up to 96 h. Powder X-ray diffraction and BET nitrogen adsorption-desorption derived surface area data are reported for the bare materials and for those loaded with low (

During the preparation of multi-component model membranes, a primary consideration is that compositional homogeneity should prevail throughout the suspension. Some conventional sample preparation methods pass the lipid mixture through an intermediary, solvent-free state. This is an ordered, solid state and may favor the demixing of membrane components. A new preparative method has been developed which is specifically designed to avoid this intermediary state. This novel strategy is called rapid solvent exchange (RSE) and entails the direct transfer of lipid mixtures between organic solvent and aqueous buffer. RSE liposomes require no more than a minute to prepare and manifest considerable entrapment volumes with a high fraction of external surface area. In phospholipid/cholesterol mixtures of high cholesterol content, suspensions prepared by more conventional methods reveal evidence of artifactual demixing, whereas samples prepared by rapid solvent exchange do not. The principles which may lead to artifactual demixing during conventional sample preparation are discussed.

The linearized cloudpoint curve correlation presented by Boom et al. [Polymer, 1993, 34, 2348] is revised. Boundaries for the validity of the linearized cloudpoint correlation are given for which an interpretation from the Flory-Huggins theory is possible. The distinction between liquid-liquid and solid-liquid demixing by this correlation must also be subjected to some constraints, although the slope in the correlation still offers a good way to distinguish between solid-liquid and liquid-liquid demixing. The statement, however, that concentration-dependent interaction parameters can be derived from this correlation must be rejected. The empirical rule found by Li et al. [Desalination, 1987, 62, 7955] can be rationalized on the basis of the LCC correlation.

Complex coacervation between proteins and polysaccharides is a demixing process mainly driven by electrostatic interactions. During this process many structural transitions occur, involving the formation of soluble complexes, aggregated complexes, and coacervates. The dynamic mechanism of complexation/coacervation was studied on β-lactoglobulin (BLG)/Acacia gum (AG) mixed dispersions (0.1 wt% total concentration; BLG:AG ratio of 2:1) using small angle static light scattering (SALS). Acidification of BLG/AG dispersions was induced by dissolution of 0.11 wt% glucono-δ-lactone, allowing in situ SALS measurements. Time evolution of turbidity, scattered light intensity at 46° scattering angle ( I 46 ) or slope of scattering functions at high q range revealed the existence of six pH-induced structural transitions. During BLG/AG complexation and before coacervation took place, scattering profiles displayed a monotonic decrease of I ( q ) as a function of q. A correlation peak in the scattering functions was only observed when coacervates appeared in the system. The wave vector q max corresponding to the maximum in scattered intensity first shifted toward larger q values, indicating an increasing number of coacervates, then shifted toward smaller q values, as a consequence of the system coarsening. The power laws q max ∼ t − α and I max ∼ t − β gave values of 1.9 and 9.2, respectively, values much larger than those expected for intermediate and late stages of spinodal decomposition. From these results, it was concluded that complex coacervation between BLG and AG was a nucleation and growth type process. In addition, the temporal evolution of I 46 followed power laws with two different exponents. First exponent corresponding to BLG/AG complexation was 3.0 ± 0.3 and indicated a diffusion-controlled growth mechanism. Second exponent corresponding to the initiation of phase separation to the coacervation process was 6.5 ± 0.3 and revealed an interfacially-controlled growth mechanism.

This paper describes the synthesis of two tri-phenylamine monomers (hole conducting) and one triazine monomer (electron conducting) which differ in their copolymerization parameters because of their styrene and vinyl ester nature. A blend of triphenylamine monomer and poly-(ethylene glycol) and mixtures of both types of monomers (triphepylamine and triazine) were illuminated through a line mask, creating laterally modulated radicals, thus leading to lateral demixing. The experiments with mixtures of triphenylamine and triazine monomers show that the concentration of p- or n-type polymers can be modulated laterally in a controlled way.

Sodium adsorption ratio SAR defined as SAR = (Na) / V w(Ca+Mg)/2 here concentrations of cations in solution are expressed in meq/L has long been considered as correlated to exchangeable sodium percentage (ESP) on clay minerals or soil exchange complex, and as the key concept to explain swelling of clay minerals and the difficulties of reclaiming salt-affected soils. Though its basis is empirical, it was alleged to be theoretically justified on the basis of ion exchange, derived from the Gapon convention. However, it has long been challenged on the basis of both field observations and experimental evidence : it fails to account for the fact that calcium and magnesium do not play the same role, while potassium is absent from the formula ; calcium concentration must be “corrected “when calcite is present etc. There exist specific ion effects. Experimental measurements of the decrease of permeability when solutions are diluted led Quirk and Schofield (1955) to define the concept of critical threshold, and to show that potassium and magnesium play an intermediate role between sodium and calcium. This threshold is simply determined by the concentration of calcium, irrespective of the value of SAR or ESP. Indeed, demixing of Ca-Na clay minerals during ion exchange, a phenomenon well known since Glaeser and Mering (1954), implies that there exists an interaction between adjacent sites. This undermines the theoretical basis of SAR : the derivation of SAR from ion exchange equilibria implies to use an equilibrium constant. This parameter is no more constant if demixing occurs. The results obtained are positive : demixing leads to expulsion of sodium from inner exchange surfaces and its replacement by calcium, according to the “three crystals pore”proposed by Quirk (2003b). Sodium can then be more easily leached, as permeability is maintained by clusters of Ca-sites. Calcium concentration in solution appears thus as the simpler parameter to guide saltaffected soils reclamation when swelling clays are present.

Although TiN and NbN are known to form a complete quasibinary solid solution, it was found that upon nitridation of Ti/Nb or annealing of (Ti,Nb)N alloys the formation of large lamellae occurs, which could be optically distinguished by their golden yellow (Ti-rich) and light yellow (Ti-poor) colour. Such structures at much smaller scales are known to result from spinodal decomposition. In order to characterize the decomposition process, the samples were investigated by wavelength-dispersive electron probe microanalysis. The measurement conditions were adjusted in order to account for the Ti LI and N Ka overlap, as well as to take an appropriate mass absorption coefficient for N in Nb into consideration. Different acceleration voltage for electron probe microanalysis were applied, which showed that the problem can be overcome by tuning the measurement conditions.

In any lipid bilayer membrane, there is an upper limit on the cholesterol concentration that can be accommodated within the bilayer structure; excess cholesterol will precipitate as crystals of pure cholesterol monohydrate. This cholesterol solubility limit is a well-defined quantity. It is a first-order phase boundary in the phospholipid/cholesterol phase diagram. There are many different solubility limits in the literature, but no clear picture has emerged that can unify the disparate results. We have studied the effects that different sample preparation methods can have on the apparent experimental solubility limit. We find that artifactual demixing of cholesterol can occur during conventional sample preparation and that this demixed cholesterol may produce artifactual cholesterol crystals. Therefore, phospholipid/cholesterol suspensions which are prepared by conventional methods may manifest variable, falsely low cholesterol solubility limits. We have developed two novel preparative methods which are specifically designed to prevent demixing during sample preparation. For detection of the cholesterol crystals, X-ray diffraction has proven to be quantitative and highly sensitive. Experiments based on these methods yield reproducible and precise cholesterol solubility limits: 66 mol% for phosphatidylcholine (PC) bilayers and 51 mol% for phosphatidylethanolamine (PE) bilayers. We present evidence that these are true, equilibrium values. In contrast to the dramatic headgroup effect (PC vs. PE), acyl chain variations had no effect on the cholesterol solubility limit in four different PC/cholesterol mixtures.

We study the demixing transition of mixtures of equal size hard spheres and dipolar hard spheres using computer simulation and integral equation theories. Calculations are carried out at constant pressure, and it is found that there is a strong correlation between the total density and the composition. The critical temperature and the critical total density are found to increase with pressure. The critical mole fraction of the dipolar component on the contrary decreases as pressure is augmented. These qualitative trends are reproduced by the theoretical approaches that on the other hand overestimate by far the value of the critical temperature. Interestingly, the critical parameters for the liquid-vapor equilibrium extrapolated from the mixture results in the limit of vanishing neutral hard sphere concentration agree rather well with recent estimates based on the extrapolation of charged hard dumbbell phase equilibria when dumbbell elongation shrinks to zero [G. Ganzenmüller and P. J. Camp, J. Chem. Phys. 126, 191104 (2007)], Dirección General de Investigación Científica y Técnica under Grant No. MAT2007-65711-C04-04 Dirección General de Universidades e Investigación de la Comunidad de Madrid under Grant No. S0505/ESP/0299 and Program MOSSNOHO-CM.

Hydrogels based on N-isopropylacrylamide and sodium acrylate as ionic comonomer were synthesized by free radical polymerization in water using N,N′-methylenebisacrylamide as crosslinker and ammonium persulfate as initiator. The glass transition of dried copolymers poly(N-isopropylacrylamide) (PNIPA) and poly(sodium acrylate) (SA) gels and demixing/mixing transition of PNIPA-SA hydrogels swollen with increasing amounts of water were studied using conventional differential scanning calorimetry. In the crosslinked polymers, the glass transition linearly increases, and the transition range becomes broader, with increasing crosslinker content. Increasing content of ionic comonomer also produces an increase of glass transition temperature, which moves to higher temperatures with higher sodium acrylate fraction. The influence of chemical structure of PNIPA-SA hydrogels on the lower critical solution temperature (LCST) of PNIPA-SA/water mixtures during heating and cooling was quantified as function of the content of the crosslinker and the ionic comonomer, as well as water content of the hydrogel in the range from 95 to 70 wt%. At parity of water content, the LCST occurs at higher temperatures for gels containing higher amounts of sodium acrylate. Similarly, the introduction of N,N′-methylenebisacrylamide causes an increase of the LCST, which grows with increasing of crosslinking degree of the hydrogel.

The demand for understanding the physical role of gangliosides in membranes is pressing, due to the high number of diverse and crucial biological functions in which they are involved, needing a unifying thread. To this purpose, model systems including gangliosides have been subject of extensive structural studies. Although showing different levels of complication, all models share the need for simplicity, in order to allow for physico-chemical clarity, so they keep far from the extreme complexity of the true biological systems. Nonetheless, as widely agreed, they provide a basic hint on the structural contribution specific molecules can pay to the complex aggregate. This topic we address in the present review. Gangliosides are likely to play their physical role through metamorphism, cooperativity and demixing, that is, they tend to segregate and identify regions where they can dictate and modulate the geometry and the topology of the structure, and its mechanical properties. Strong three-dimensional organisation and cooperativity are exploited to scale up the local arrangement hierarchically from the nano- to the mesoscale, influencing the overall morphology of the structure.

Significant progress is being made in the photovoltaic energy conversion using organic semiconducting materials. One of the focuses of attention is the morphology of the donor-acceptor heterojunction at the nanometer scale, to ensure efficient charge generation and loss-free charge transport at the same time. Here, we present a method for the controlled, sequential design of a bilayer polymer cell architecture that consists of a large interface area with connecting paths to the respective electrodes for both materials. We used the surface-directed demixing of a donor conjugated/guest polymer blend during spin coating to produce a nanostructured interface, which was, after removal of the guest with a selective solvent, covered with an acceptor layer. With use of a donor poly(p-phenylenevinylene) derivative and the acceptor C60 fullerene, this resulted in much-improved device performance, with external power efficiencies more than 3 times higher than those reported for that particular material combination so far.